JPH07258824A - Base material coated with boron nitride containing film - Google Patents

Abstract

PURPOSE:To obtain a base material excellent in chemical stability as well as in hardness and toughness. CONSTITUTION:This base material is a base material 10 coated with boron nitride containing film and can be obtained by coating a base material 1 with a boron nitride containing film 2 which has infrared absorption peaks observed by an infrared spectroscopic method at least at the wave numbers of about 1080cm<-1> and about 1380cm<-1> and in which the intensity ratio of respective absorption peaks at the wave numbers of about 1380cm<-1> and about 1080cm<-1> 15 regulated to 0.15-3.5. As the crystal structure of BN in the boron nitride containing film formed on the base material, c-BN and h-BN exist in the form of a mixture, and as a result, superior hardness due to c-BN can be provided, and further, the inferior brittleness can be improved because h-BN has a property of cleaving in a c-axis direction.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a boron nitride-containing film-coated substrate, and more particularly, to improve friction, wear, lubrication performance, etc. in cutting tools, dies, magnetic heads or various sliding parts. The present invention relates to a substrate coated with a boron nitride-containing film.

[0002]

2. Description of the Related Art Boron nitride (BN) has a structure similar to that of hexagonal graphite (h-
BN), cubic zinc blende type (c-BN), or hexagonal wurtzite type (w-BN). c-BN has high hardness and thermal conductivity second only to diamond, and is superior in thermal and chemical stability to diamond. Therefore, it is a material for heat sinks and heat sinks that require wear resistance such as cutting tools. Has been applied to.

However, since c-BN is artificially synthesized under high temperature and high pressure, the production cost thereof is very high and the form of c-BN synthesized is powder or granules. As a result, the range of application is limited. So, c-BN and w-BN at low temperature,
Attempts to synthesize thin films were made using various PVD methods (Physical
Vapor Deposition) and CVD (Chemical Vapor Depos
ition).

An example of research by the thermal CVD method will be described. In this method, a substrate is placed in a reaction chamber, and a gas containing boron (B) and a source gas containing nitrogen (N) are introduced into the reaction chamber. By heating the substrate to a temperature close to 1000 ° C., the raw material gas is thermally decomposed to form a film on the surface of the substrate. However, this method has a drawback that the type of substrate is limited because the substrate is required to have heat resistance. For example, high speed tool steel (high speed steel)
It is impossible to use, as a substrate, such a product as described above that causes hardness deterioration at a temperature of about 500 ° C. or higher, or a mold that does not allow dimensional accuracy due to deformation at high temperatures. Further, although h-BN has been easily synthesized by the CVD method, an example of synthesizing c-BN has not been reported yet, and the fact is that it is in the research stage.

Further, in the PVD method, a method of sputtering a target made of boron nitride by irradiating a laser to form a boron nitride-containing film on the surface of the substrate has been tried, but like the CVD method, Synthesis of c-BN was not possible. In recent years, many attempts have been made to synthesize c-BN at low temperature by positively using ions and plasma.
Japanese Patent Publication No. 59863 also proposes a method of synthesizing c-BN at a low temperature by using vacuum vapor deposition and ion irradiation in combination. According to this, c-
Thin film synthesis of BN at low temperature becomes possible, and application of BN film can be expanded.

[0006]

The use of plasma, ions, etc. has opened the way to the synthesis of c-BN films at low temperatures, but in practical use, the adhesion and toughness between the substrate and the film have to be improved. It becomes a big problem. That is, although it was possible to synthesize a c-BN film at a low temperature by the method described above,
The BN film is a brittle substance, and during use, the film is likely to be cracked, and the film is chipped, so that practically sufficient characteristics are not obtained.

The present invention has been made in view of the above-mentioned problems, and contains a boron nitride containing a BN film on a substrate, which has practically sufficient toughness and hardness and is excellent in chemical stability. The purpose is to provide a film-coated substrate.

[0008]

Means for Solving the Problems] To achieve the above object, the present invention has a wave number of at least about 1080 cm ^-1 to about 1380 cm ^-1 of the infrared absorption peak by infrared spectroscopy, approximately 1380 cm ^{- The} substrate is coated with a boron nitride-containing film in which the intensity ratio of absorption peaks at wave numbers of ¹ and about 1080 cm ⁻¹ is in the range of 0.15 to 3.5.

The substrate used in the substrate coated with the boron nitride-containing film of the present invention is not particularly limited, and examples include substrates made of polyethylenes such as polycarbonate and polyethylene terephthalate, polymers such as polyimide, and high speed tool steel. Materials such as cemented carbide, metals such as carbon steel, and ceramics such as alumina, silicon nitride, and silicon carbide can be used.

The boron nitride-containing film in the boron nitride-containing film-coated substrate of the present invention can have a high hardness as long as it has a c-BN crystal structure, and h
If it has a crystal structure of -BN, the brittleness of c-BN can be improved by the cleavability of h-BN, and a film having high hardness and toughness as a whole can be obtained. , C-BN and h-BN are preferably mixed. When BN having these structures was analyzed by infrared spectroscopy, c-BN had a wave number of about 1080 cm ⁻¹ and h
-BN has absorption peaks at wave numbers of about 1380 cm ^-1 and about 780 cm ^-1 , respectively. Therefore, c-BN and h-
The mixing amount with BN is the infrared absorption peak intensity ratio (1380c
m ⁻¹ peak intensity / 1080 cm ⁻¹ peak intensity). That is, the infrared absorption peak intensity ratio is
It is necessary that the entire film exists in the range of 0.15 to 3.5, preferably 0.5 to 2.5. This is because when the amount of h-BN is too large, the film becomes too soft, and when the amount of c-BN is too large, the toughness of the film is inferior. Therefore, the mixing amount is adjusted by the infrared absorption peak intensity ratio.

The infrared absorption peak intensity ratio is 0.15 to 3.5.
The film included in 1 may be a single layer or a plurality of layers. The infrared absorption peak intensity ratio is 0.15 to 0.5 or 2.5 to 3.5.
In the case of the above, it is preferable that a plurality of layers having different infrared absorption peak intensity ratios are formed so that the peak intensity ratio exists in the above range as a whole film. Further, the peak intensity ratio at this time may be changed gradually or stepwise such as increasing or decreasing, but it is preferable that the ratio is increased from the substrate side to the film surface side.

In the substrate coated with a boron nitride-containing film of the present invention, a region in which atoms constituting the substrate, nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed may be formed on the surface of the substrate. Such a region is formed, for example, by forming a boron nitride film on a substrate by using vacuum vapor deposition or sputtering of boron and nitrogen ion irradiation in combination.
Can be formed.

Further, the substrate may have a region in which nitrogen atoms are implanted on the surface of the substrate. That is, a region in which the atoms forming the substrate and the nitrogen atoms are mixed may be formed on the surface of the substrate. Such a region can be formed, for example, by irradiating the substrate with nitrogen ions. The irradiation energy of nitrogen ions at that time is
0.1 KeV to 40 KeV is preferable. If it is less than 0.1 KeV, the penetration depth of implanted nitrogen ions into the substrate is too shallow to sufficiently improve the adhesion of the film. On the other hand, if it is greater than 40 KeV, the substrate becomes This is not preferable because it causes excessive thermal damage and deteriorates the characteristics of the substrate. The number of nitrogen ions with which the substrate is irradiated is 1 × 10 ¹⁴ / cm ² to 1 × 10 ¹⁹ / cm ^2.
Is preferred. When 1 × 10 is ¹⁴ pieces / cm less than ^2, fewer nitrogen atoms distributed in the substrate, the effect of the present invention is not sufficiently exhibited, 1 × and 10 is larger than ¹⁹ pieces / cm ^2, the ion to the substrate Irradiation causes excessive damage, which deteriorates the characteristics of the substrate, which is not preferable.

Further, in the present invention, a region in which the atoms and nitrogen atoms forming the substrate are mixed is formed on the surface of the substrate, and further, the atoms forming the substrate and boron nitride are contained on the surface of the region. A region in which nitrogen atoms and boron atoms which form the film are mixed may be formed. As described above, such a region is formed by first irradiating the substrate with nitrogen ions, and then by vacuum deposition or sputtering of boron and nitrogen ion irradiation on the region irradiated with nitrogen ions. It can be formed by forming a film.

In the present invention, the c-
The crystal structure of BN or h-BN is obtained by independently changing the irradiation energy of irradiation ions, the ion species, the current density, and the ratio of boron atoms and nitrogen atoms reaching the substrate (B / N composition ratio). Or it can control by changing in combination. For example, the ion irradiation energy may be kept constant and the B / N composition ratio may be changed continuously or intermittently to form a film, or the ion irradiation energy may be kept constant while keeping the B / N composition ratio constant. It may be changed continuously or intermittently. Further, the irradiation energy and current density of ions are kept constant, and the B / N composition ratio is changed continuously or intermittently, or the irradiation energy and current density of ions are continuously or intermittently changed at the same B / N composition ratio. May be changed. Furthermore, both the irradiation energy of the ions and the B / N composition ratio can be changed continuously or intermittently, and the ion species can be selected appropriately. For example, when nitrogen ions are used, when the irradiation energy is 2 KeV or more, and when the current density is 0.1 mA / cm ² or less, the crystal growth of c-BN increases as the B / N composition ratio becomes larger than 1. It is accelerated, and conversely, the closer the B / N composition ratio is to 1, the more easily h-BN is synthesized. When the current density is higher than 0.1 mA / cm ² , the crystal growth of c-BN is promoted regardless of the B / N composition ratio. Further, when nitrogen ions having an irradiation energy smaller than 2 KeV are used, the crystal growth of c-BN is promoted as the B / N composition ratio becomes closer to 1, and the B / N composition ratio becomes larger than 1 regardless of the current density. I see, h-B
N is easily synthesized. It is also possible to control the crystal structure of BN in the boron nitride-containing film by using a mixture of nitrogen ions and Ar ions. In that case, regardless of the current density of the ions, the B / N composition ratio is The closer to 1, the c-BN
Crystal growth is promoted, and when the B / N composition ratio is larger than 1, crystal growth of h-BN is promoted, so that it can be utilized to change the crystal structure of the boron nitride-containing film. However, when the ion irradiation energy exceeds 40 KeV, excessive defects are generated in the film, and the hardness and chemical stability of the film are deteriorated, which is not preferable, and 0.1 Ke
When it is less than V, it is difficult to form c-BN, which is not preferable. Further, when the B / N composition ratio is less than 1.0, the sputtering due to the irradiation ions of vapor-deposited boron becomes excessive, and also excessive defects are generated in the film, so that the hardness and the chemical stability of the film are deteriorated. It is not preferable because it decreases. When the B / N composition ratio is more than 60, the amount of boron nitride contained in the film becomes small, and the characteristics of the boron nitride cannot be sufficiently obtained, which is not preferable.

Further, in the present invention, the temperature of the substrate when forming the film is preferably about 60 ° C. to about 200 ° C., and about 6 ° C.
More preferred is 0 ° C to about 150 ° C. This is obtained by cooling the substrate holder. This does not change the effect of the present invention, but it is possible to use a substrate made of various materials that must avoid thermal damage.

In the present invention, the film can be formed on the substrate by appropriately using, for example, an ion vapor deposition thin film forming method, an ion plating method, and various sputtering methods. The apparatus for forming the film at this time is not particularly limited, but vacuum vapor deposition or sputtering, which is a method of easily including a high hardness c-BN structure in the BN film, and ion irradiation are performed at the same time. What can be done is preferable. For example, an apparatus capable of simultaneously performing vacuum vapor deposition and ion irradiation as shown in FIG. 3 can be used. According to this device,
Evaporated atoms of boron are highly excited by collision with irradiation ions, and c-BN crystals are easily formed. In FIG. 3, reference numeral 1 is a base, and the base holder 8 is configured so that the base 1 can be placed. Further, an evaporation source 3 and an ion source 4 are arranged at positions facing the substrate 1, respectively, and they are all housed in a vacuum container 5. The vacuum container 5 is held in a vacuum state by an exhaust device (not shown). Further, in the vicinity of the substrate holder 8, a film thickness monitor 6 capable of monitoring the vapor deposition amount of vapor deposition atoms on the substrate 1, and an ion current measuring device 7 capable of monitoring the irradiation amount of ions on the substrate 1 are provided. It is arranged. Further, a cooling pipe (not shown) for cooling the substrate 1 may be provided inside the substrate holder 8.

In the apparatus constructed as described above, the vacuum container 5 is evacuated to a predetermined degree of vacuum and held by the evacuation device. The evaporation source 3 heats and vaporizes a boron-containing substance by an electron beam, resistance or high frequency. However, when a sublimable substance is used as the boron-containing substance for vaporization by heating, the evaporation rate may not be stable, and thus the sputtering method can be used.
Moreover, the method of the ion source 4 is not particularly limited, and a Kauffman type, a bucket type, or the like can be appropriately used. The methods of the film thickness monitor 6 and the ion current measuring device 7 are not particularly limited. For example, a crystal oscillator is used as the film thickness monitor 6, and a Faraday cup or the like is appropriately used as the ion current measuring device 7. be able to.

The substrate of the present invention is placed in a vacuum container by placing the substrate on a substrate holder, and for example, 1 × 1.
After evacuation to a vacuum degree of 0 ⁻⁶ torr or less, boron is deposited on the substrate and nitrogen ion irradiation is performed to form a boron nitride-containing film. The surface of the substrate may be first irradiated with ions such as nitrogen ions, and then a film may be formed on the substrate. The irradiation angle of the ions on the substrate at this time is not particularly limited.

Examples of the method for depositing the boron-containing substance include vacuum vapor deposition or sputtering in which the boron-containing substance is heated and vaporized by an evaporation source. As the boron-containing substance vaporized or sputtered from the evaporation source, a simple substance of boron, an oxide, a nitride, a carbide, or the like can be used. Then, simultaneously with the vapor deposition or deposition of the substance, or after the vapor deposition or deposition, the ion source is irradiated with ions containing at least nitrogen. At this time, it is effective to use nitrogen ions as the ions to be irradiated, but those containing nitrogen ions and inert gas ions or hydrogen ions can be used. These can be obtained, for example, by introducing only nitrogen gas into the ion source, or introducing nitrogen gas and an inert gas or hydrogen gas. In this case, the deposited boron atoms are brought into an even more highly excited state by the inert gas ions and hydrogen ions, which has the advantage of improving the crystallinity of the film. The irradiation energy of the ions for irradiation is preferably in the range of about 0.1 KeV to about 40 KeV. Further, the composition ratio of boron atoms and nitrogen ions reaching the substrate when forming the film is preferably about 1.0 to about 60.0. The composition ratio of B / N is obtained by measuring the number of boron atoms reaching the substrate with the film thickness monitor 6 in FIG. 3 and measuring the number of ions with which the substrate is irradiated by the current measuring device 7. Can be adjusted. The film containing boron nitride is about 1380 cm ^-1 and about 108
The infrared absorption peak intensity ratio with 0 cm ⁻¹ is 0.15 to 3.5
The composition ratio may be constant in the film as long as it has the above condition, or the B / N composition ratio may be gradually or stepwise changed from the substrate side to the film surface side. Is also possible. The thickness of the boron nitride-containing film at this time is not particularly limited, but is 0.05 μm.
It is preferably 10 μm.

[0021]

According to the boron nitride-containing film-coated substrate of the present invention,
An infrared absorption peak by infrared spectroscopy of at least about 108
Has a wave number of between 0 cm ^-1 and about 1380 cm ^-1, about 138
Since coating the boron nitride-containing film having an intensity ratio of absorption peaks 0.15 to 3.5 at a wave number of 0 cm ^-1 and about 1080 cm ^-1 on a substrate, the membrane of the crystal structure, the desired ratio Therefore, c-BN and h-BN are mixed. That is, it has a high hardness based on c-BN, and the brittleness of c-BN is eliminated by the softness cleaved in the c-axis direction based on h-BN, resulting in high hardness and toughness as a whole.

Further, when a region in which atoms constituting the substrate, nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed is formed on the surface of the substrate, the interface between the substrate and the film disappears. Therefore, the adhesion of the boron nitride-containing film to the substrate is improved. Further, when the substrate has a region in which nitrogen atoms are implanted on the surface of the substrate, the wettability of the boron nitride-containing film to the substrate is improved and the lattice constant mismatch between the substrate and the film By the improvement, the internal stress generated at the time of film formation is relaxed, and the adhesion of the boron nitride-containing film to the substrate is improved.

Further, the substrate has a region in which nitrogen atoms are implanted on the surface of the substrate, and atoms constituting the substrate, nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed on the surface of the region. When the formed region is formed, the wettability is improved, the internal stress generated between the substrate and the film is further relieved, and the adhesion of the boron nitride-containing film to the substrate is significantly improved. Becomes

[0024]

EXAMPLES Examples of boron nitride-containing film-coated substrates according to the present invention are shown below. Example 1 First, the silicon substrate 1 shown in FIG.
0)) was housed in the vacuum container of the ion deposition thin film forming apparatus shown in FIG. 3, and the inside of the vacuum container was maintained at a vacuum degree of 5 × 10 ⁻⁷ Torr. Next, the boron pellet having a purity of 99.7% is vaporized from the electron beam evaporation source, and the silicon substrate 1
Evaporated on top. Simultaneously with this deposition, the ion source has a purity of 5N.
Was introduced into the vacuum container until the inside of the vacuum container reached 5 × 10 ⁻⁵ Torr, ionized, and irradiated with the irradiation energy of 0.2 KeV at 0 ° with respect to the normal to the substrate. At this time, the evaporation rate of boron and the irradiation rate of nitrogen ions are adjusted in consideration of the sputtering rate of nitrogen ions of boron, etc., so that the film thickness is about 500 nm and the B / N composition ratio is 5, so that the silicon substrate A boron nitride-containing film 2 was formed on the film 1. As the ion source, a bucket type ion source using a cusp magnetic field was used.

In the boron nitride-containing film coated substrate 10 thus formed, the region 1a in which silicon, nitrogen atoms and boron atoms forming the boron nitride-containing film are mixed is formed on the surface of the silicon substrate 1. , This area 1a
A boron nitride-containing film 2 is formed on the above. Example 2 Using the same substrate as in Example 1, the irradiation energy of nitrogen ions was 10 KeV and the B / N ratio was the same as in Example 1.
A boron nitride-containing film having a thickness of about 500 nm was formed so that the composition ratio was 20. Example 3 A substrate similar to that in Example 1 was used, and the irradiation energy of nitrogen ions was 10 KeV and B / N was measured in the same manner as in Example 1.
After forming a film containing boron nitride having a thickness of about 500 nm so as to have a composition ratio of 25, a film containing boron nitride having a content of about 500 nm having a nitrogen ion irradiation energy of 10 KeV and a B / N composition ratio of 1 is formed on the film. A film was formed. Example 4 Using the same substrate as in Example 1, a boron nitride-containing film of about 500 nm was formed by the same method as in Example 1 so that the irradiation energy of nitrogen ions was 2 KeV and the B / N composition ratio was 20. Then, the irradiation energy of nitrogen ions on the film was set to 2 KeV and the B / N composition ratio was set to about 50.
A 0 nm boron nitride-containing film was formed. Example 5 The same substrate as in Example 1 was used, and 1 × 10 ¹⁶ / cm ² nitrogen ions were previously implanted into the substrate at an irradiation energy of 10 KeV. Then, in the same manner as in Example 1, the nitrogen ion irradiation energy of 0.2 KeV and the B / N composition ratio = 5 were set on the substrate on which the nitrogen ions were implanted to about 5%.
A 00 nm boron nitride-containing film was formed.

As shown in FIG. 2, the boron-nitride-containing film-coated substrate 20 thus formed has silicon, nitrogen atoms and boron atoms constituting the boron nitride-containing film on the outermost surface of the silicon substrate 1. A mixed region 1a is formed, and a region 1b in which silicon and nitrogen are mixed is provided below the region 1a as a region into which nitrogen atoms are implanted.
Further, the boron nitride-containing film 2 is formed on the region 1a. Comparative Example 1 A substrate similar to that of Example 1 was used, and the irradiation energy of nitrogen ions was 0.2 KeV, B /
A boron nitride-containing film having a thickness of about 500 nm was formed so that the N composition ratio was 1. Comparative Example 2 Using the same substrate as in Example 1, and by the same method as in Example 1, irradiation energy of nitrogen ions was 10 KeV, B / N.
A boron nitride-containing film having a thickness of about 500 nm was formed so that the composition ratio was 1. Comparative Example 3 Using the same substrate as in Example 1, and by the same method as in Example 3, irradiation energy of nitrogen ions was 10 KeV, B / N.
After forming a film containing boron nitride of about 500 nm so that the composition ratio becomes 1.5, the irradiation energy of nitrogen ions is 10 KeV and the B / N composition ratio becomes 1 on the film.
A film containing boron nitride having a thickness of about 500 nm was formed. Comparative Example 4 Using the same substrate as in Example 1, and by the same method as in Example 3, irradiation energy of nitrogen ions was 10 KeV, B / N.
A boron nitride-containing film having a thickness of about 500 nm was formed so that the composition ratio was 1. Comparative Example 5 Using the same substrate as in Example 1, and by the same method as in Example 3, irradiation energy of nitrogen ions was 10 KeV, B / N.
After forming a film containing boron nitride having a thickness of about 500 nm so that the composition ratio becomes 2, a nitrogen ion irradiation energy of 10 KeV and a B / N composition ratio of about 5 are formed on the film.
A 00 nm boron nitride-containing film was formed. Comparative Example 6 Using the same substrate as in Example 1, and by the same method as in Example 3, irradiation energy of nitrogen ions was 10 KeV, B / N.
After forming a boron nitride-containing film of about 500 nm so that the composition ratio becomes 20, a nitrogen ion irradiation energy of 10 KeV and a B / N composition ratio = 15 are formed on the film.
A film containing boron nitride having a thickness of about 500 nm was formed. Comparative Example 7 Using the same substrate as in Example 1, and by the same method as in Example 1, without previously irradiating the substrate with nitrogen ions, irradiation energy of nitrogen ions was 0.2 KeV, B / N composition ratio =
A film containing boron nitride having a thickness of about 500 nm was formed so as to have a thickness of 5.

The hardness of the film thus formed is 1
Each was measured by a Vickers hardness meter with 0 g load.
In addition, the above film, the silicon substrate as a reference,
The infrared absorption peak was measured by FT-IR (Fourier transform infrared spectroscopy), and at that time, 1380 cm ^-1 and 1080
The intensity ratio of the absorption peak at the wave number of cm ⁻¹ was obtained. Further, the materials of Examples 3 and 4 and Comparative Examples 3 to 6 were heated in the atmosphere, and the temperature at which the weight change due to the oxidation of the film was generated was determined. The results are shown in Table 1.

[0028]

[Table 1]

As is clear from Table 1, the membranes of the examples are
Each had a peak intensity ratio within the range indicated by the present invention, but none of the comparative examples except Comparative Examples 1 and 7 had a peak intensity ratio within the range indicated by the present invention. On the other hand, the films of Examples and the films of Comparative Examples 1, 6 and 7 all showed a Vickers hardness of 3000 kg / cm ² or more, but the films of Comparative Examples 2, 4 and 5 had a Vickers hardness of 1500 kg / cm ^2. It only showed values below cm ² . Further, in Comparative Examples 1 and 3, cracks were formed at the tips of the indentations during Vickers hardness measurement, whereas no cracks were observed at the tips of the indentations in any of the films of the examples.

Further, the adhesion of the films of Example 5 and Comparative Example 7 was evaluated with a scratch tester by applying a diamond indenter load of 0.
The load at which the AE signal sharply increased was measured by continuously increasing from N. As a result, in Example 5, 45N,
In Comparative Example 7, a value of 36 N was shown, and it was found that Example 5 in which the substrate was previously irradiated with nitrogen ions was superior in adhesiveness to Comparative Example 7 in which ion irradiation was not performed.

Therefore, 1380 cm ^-1 and 1080 cm ^-1
It was found that the film having an absorption peak intensity ratio at the wave numbers of and in the range of the present invention, that is, in the range of 0.15 to 3.5 is excellent in hardness, toughness, and chemical stability. It was Further, in a boron nitride film having a region in which nitrogen atoms are implanted on the surface of the substrate and having a region in which silicon and nitrogen atoms and boron atoms forming the boron nitride-containing film are mixed on the surface of the region It was found that it was also extremely excellent in sex.

[0032]

According to a boron nitride-containing film-coated substrate of the present invention, has a wave number of at least about 1080 cm ^-1 to about 1380 cm ^-1 of the infrared absorption peak by infrared spectroscopy, and about 1380 cm ^-1 Since a boron nitride-containing film having an absorption peak intensity ratio of 0.15 to 3.5 at a wave number of 1080 cm ⁻¹ is coated on a substrate, a crystalline structure of c-BN and h-BN at a desired ratio is obtained. Will be mixed. Therefore, it has a high hardness based on c-BN, the brittleness of c-BN is eliminated by the softness cleaved in the c-axis direction based on h-BN, and it has excellent hardness and toughness as a whole, In addition, a chemically stable substrate can be obtained.

Further, in the case where a region in which atoms constituting the substrate, nitrogen atoms constituting the film containing boron nitride and boron atoms are mixed is formed on the surface of the substrate, the interface between the substrate and the film disappears. The adhesion of the boron nitride-containing film to the substrate can be improved. Further, when the substrate surface has a region in which nitrogen atoms are implanted, the wettability of the boron nitride-containing film to the substrate can be improved, and the lattice constant mismatch between the substrate and the film can be improved. The internal stress generated during the film formation can be relaxed, and the adhesion of the boron nitride-containing film to the substrate can be improved.

Further, the substrate surface has a region into which nitrogen atoms have been implanted, and a region in which atoms constituting the substrate and nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed is formed on the surface of the region. In such a case, the wettability is improved, the internal stress generated between the substrate and the film can be further relaxed, and the adhesion of the boron nitride-containing film to the substrate can be significantly improved.

Therefore, it has a high hardness based on c-BN, the brittleness of c-BN is eliminated by the softness cleaved in the c-axis direction based on h-BN, and the hardness and toughness are excellent and the chemical property is high. A stable base material can be obtained, and it can be used in various applications such as tools, molds, and magnetic heads.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing an example of a boron nitride-containing film-coated substrate according to the present invention.

FIG. 2 is a schematic cross-sectional view showing another embodiment of a boron nitride-containing film-coated substrate according to the present invention.

FIG. 3 is a schematic cross-sectional view of a main part of a film forming apparatus used for manufacturing a boron nitride-containing film-coated substrate according to the present invention.

[Explanation of symbols]

 1 Silicon Substrate (Base) 1a Si, B, N Mixed Area 1b Si, N Mixed Area (N Implanted Area) 2 Boron Nitride Containing Film 3 Evaporation Source 4 Ion Source 5 Vacuum Container 6 Thickness Monitor 7 Ion Current Monitor 8 Substrate holder 10, 20 Boron nitride-containing film-coated substrate

Claims (4)

[Claims] 1. An infrared absorption peak by infrared spectroscopy of at least about 1080 cm ^-1 and about 1380 cm ^{-1 on the} substrate.
It has about 1380cm ^-1 and about 1080cm ^-1
A substrate coated with a boron nitride-containing film, characterized by being coated with a boron nitride-containing film having an absorption peak intensity ratio in the wave number of 0.15 to 3.5. 2. The substrate coated with a boron nitride-containing film according to claim 1, wherein the substrate has a region in which atoms constituting the substrate, nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed on the surface of the substrate. 3. The boron nitride-containing film-coated substrate according to claim 1, wherein the substrate has a region in which nitrogen atoms are implanted on the surface of the substrate. 4. The substrate has a region in which nitrogen atoms are implanted on the surface of the substrate, and atoms constituting the substrate, nitrogen atoms and boron atoms constituting the boron nitride-containing film are mixed on the surface of the region. The boron-nitride-containing film-coated substrate according to claim 1, which has a formed region.